Alkyne compounds

ABSTRACT

The present invention relates to alkyne compounds of the formula 
 
P 1 —Y 1 -A 1 -Y 3 -(T 1 -B 1 -) m -T 3 -C≡C-T 4 -(B 2 -T 2 -) n -Y 4 -A 2 -Y 2 —P 2   (I) 
in which 
         P 1 , P 2  are each, independently of one another, hydrogen, C 1 -C 12 -alkyl, a polymerizable group or a group suitable for polymerization or a radical which carries a polymerizable group or a group suitable for polymerization,    Y 1 , Y 2 , Y 3 , Y 4  are each, independently of one another, a linking unit,    B 1 , B 2  are each, independently of one another, —C≡C— or a linking group as defined for Y 1  to Y 4 ,    A 1 , A 2  are each, independently of one another, a single chemical bond or a spacer having from one to  30  carbon atoms,    T 1 , T 2 , T 3 , T 4  are each, independently of one another, a divalent saturated or unsaturated carbocyclic or heterocyclic radical, and    m, n are each, independently of one another,  0  or  1,  
 
with the proviso that at least one of the linking units Y 3  or Y 4  is a group —O—CO—O—, —O—CO—N(R)—, —(R)N—CO—O— or —(R)N—CO—N(R)—. 
The invention further relates to nonpolymerizable and polymerizable liquid-crystalline compositions comprising at least one alkyne compound of the formula I according to the invention, the use of these nonpolymerizable and polymerizable liquid-crystalline compositions for producing optical components, the use of the polymerizable liquid-crystalline compositions for printing or coating substrates, for preparing dispersions and emulsions, for producing films and pigments and optical components, printed or coated substrates, dispersions and emulsions, films and pigments of this type.

The present invention relates to alkyne compounds of the formula IP¹—Y¹-A¹-Y³-(T¹-B¹-)_(m)T³-C≡C-T⁴-(B²-T²-)_(n)-Y⁴-A²-Y²-P²  (I)in which

-   -   P¹, P² are each, independently of one another, hydrogen,        C₁-C₁₂-alkyl, a polymerizable group or a group suitable for        polymerization or a radical which carries a polymerizable group        or a group suitable for polymerization,    -   Y¹, Y², Y³, Y⁴ are each, independently of one another, a single        chemical bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —CO—N(R)—,        —(R)N—CO—, —O—CO—O—, —O—CO—N(R)—, —(R)N—CO—O— or —(R) N—CO—N        (R)—,    -   B¹, B² are each, independently of one another, —C≡C—, a single        chemical bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —CO—N(R)—,        —(R)N—CO—, —O—CO—O—, —O—CO—N(R)—, —(R)N—CO—O— or —(R)N—CO—N(R)—,    -   R, at each occurrence and independently of the meaning in Y¹ to        Y⁴, B¹ and B², is hydrogen or C₁-C₄-alkyl,    -   A¹, A² are each, independently of one another, a single chemical        bond or a spacer having from one to 30 carbon atoms,    -   T¹, T², T³, T⁴ are each, independently of one another, a        divalent saturated or unsaturated carbocyclic or heterocyclic        radical, and    -   m, n are each, independently of one another, 0 or 1,        with the proviso that at least one of the linking units Y³ or Y⁴        is a group —O—CO—O—, —O—CO—N(R)—, —(R)N—CO—O— or —(R)N—CO—N(R)—.

The invention further relates to nonpolymerizable or polymerizableliquid-crystalline compositions comprising at least one alkyne compoundof the formula I according-to the invention, the use of thesenonpolymerizable and polymerizable liquid-crystalline compositions forproducing optical components, the use of the polymerizableliquid-crystalline compositions for printing or coating substrates, forpreparing dispersions and emulsions, and for producing films or pigmentsand optical components, printed or coated substrates, dispersions andemulsions, films and pigments of this type.

Because of their comparatively high birefringent properties,liquid-crystalline systems comprising alkyne compounds are of interest,inter alia, for broadband reflective elements in electroopticalapplications. A variety of such alkyne derivatives and applicationsthereof are described, for example, in the documents

-   DE 39 05 932 A1, DE 199 26 044 A1, DE 100 64 291 A1,-   FR 2 234 261, GB 2 155 465 A, GB 2 334 718 A, GB 2 351 734 A,-   JP 11-080090 A, JP P2000-281628A, JP P2000-281629A,-   EP 0 727 473 A2, EP 0 930 286 A1, EP 0 968 988 A1,-   EP 1 054 001 A1 and the publications of A. P. Davey et al. (J.    Mater. Chem., 1997, 7(3), 417-420) and N. Leroux and L.-C. Chien    (Liquid Crystals, 1996, Vol. 21, No. 2, 189-195).

In addition to other criteria which usually have to be met byliquid-crystalline materials, such as a very high anisotropy of thedielectric properties and a very high resistivity, their phase behavioris also important. These materials should exhibit the desiredliquid-crystalline behavior over a broad temperature range so as toprovide, for example, a very wide choice in terms of processingconditions.

It is therefore an object of the present invention to provide furtheralkyne compounds which have comparatively high birefringent propertiesand are suitable for preparing liquid-crystalline compositions and whichexhibit, themselves or in the form of such compositions, a phase widthwhich is sufficiently large for processing.

We have found that this object is achieved by the alkyne compounds ofthe formula I described at the outset.

C₁-C₁₂-Alkyl radicals for P¹ and P² in formula I are branched orunbranched C₁-C₁₂-alkyl chains, for example methyl, ethyl, n-propyl,1-methylethyl, n-butyl, 1-methylpropyl-, 2-methylpropyl,1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl andn-dodecyl.

Preferred alkyl radicals for P¹ and P² are the branched or unbranchedC₁-C₆-alkyl chains, for example methyl, ethyl, n-propyl, 1-methylethyl,n-butyl, 1-methylpropyl-, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,1-ethylpropyl and n-hexyl.

Polymerizable groups or groups suitable for polymerization or radicalswhich carry a polymerizable group or a group suitable for polymerization(such groups or radicals are hereinafter also simply called “reactiveradicals”) which are suitable for P¹ and P² are in particular:

where R¹ to R³ may be identical or different and are each hydrogen orC₁-C₄-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl or tert-butyl.

Particularly suitable reactive radicals for P¹ and P² are 1-methylvinyland vinyl. Within the context of these radicals, particularly suitablelinking units Y¹ and Y² are carboxyl, —CO—O— or —O—CO—, and a singlechemical bond. Particularly suitable moieties P¹—Y¹— and —Y²—P²comprising reactive radicals are therefore acrylate, methacrylate andvinyl.

Of the reactive radicals, the cyanates can spontaneously trimerize tocyanurates. The other groups mentioned usually require further compoundscontaining complementary reactive radicals for polymerization. Thus, forexample, isocyanates can polymerize with alcohols to give urethanes andwith amines to give urea derivatives. Thiiranes and aziridines behavesimilarly.

Carboxyl groups can be condensed to give polyesters and polyamides. Themaleimido group is particularly suitable for free-radicalcopolymerization with olefinic compounds, for example styrene, orcompounds comprising styrene structural elements.

The reactive radicals and the reactive radicals complementary theretomay be present in a single alkyne compound according to the invention orin an additional alkyne compound according to the invention.

Alternatively, the complementary reactive radicals may be present infurther compounds not according to the invention. Examples of the latterare polyhydric alcohols, such as ethylene glycol, propylene glycol andtheir more highly condensed representatives, for example diethyleneglycol, triethylene glycol, dipropylene glycol, tripropylene glycoletc., butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylatedphenolic compounds, such as ethoxylated or propoxylated bisphenols,cyclohexanedimethanol, alcohols with a functionality of three or more,such as glycerol, trimethylolpropane, butanetriol, trimethylolethane,pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol,mannitol and the corresponding alkoxylated, especially ethoxylated andpropoxylated, alcohols. Further suitable compounds are amino alcoholswhich are derived from the abovementioned alcohols by replacing one ormore hydroxyl groups by amino groups.

Suitable C₁-C₄-alkyl groups for R in the groups —CO—N(R)—, —(R)N—CO—,—O—CO—N(R)—, —(R)N—CO—O— and —(R)N—CO—N(R)— shown below the linkingunits Y¹ to Y⁴ and B¹, B² are methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl and tert-butyl. If one or two radicals Rare present in one of the linking units Y¹ to Y⁴ and B¹, B², radicals Rwhich may be present in the other units may be identical or different.The same applies if two radicals R are present in one unit.

Suitable spacers A¹ and A² are all groups known for this purpose to aperson skilled in the art. The spacers usually contain one to 30,preferably one to 12, particularly preferably one to six, carbon atomsand consist of predominantly linear aliphatic groups. The spacers may beinterrupted in the chain, for example by non-adjacent oxygen or sulfuratoms or imino or alkylimino groups, for example methylimino groups.Suitable substituents for the spacer chain are fluorine, chlorine,bromine, cyano, methyl and ethyl.

Examples of representative spacers are:

where u, v and w are integers and u is 1 to 30, preferably 1 to 12, v is1 to 14, preferably 1 to 5, and w is 1 to 9, preferably 1 to 3.

Preferred spacers are ethylene, propylene, n-butylene, n-pentylene andn-hexylene.

The radicals T¹ to T⁴ are ring systems which may be substituted byfluorine, chlorine, bromine, cyano, hydroxyl, formyl, nitro,C₁-C₂₀-alkyl, C₁-C₂₀-alkoxy, C₁-C₂₀-alkoxycarbonyl,C₁-C₂₀-monoalkylaminocarbonyl, C₁-C₂₀-alkylcarbonyl,C₁-C₂₀-alkylcarbonyloxy or C₁-C₂₀-alkylcarbonylamino.

Preferred radicals T¹ to T⁴ are:

In accordance with the proviso given at the outset, the alkyne compoundsof the formula I according to the invention, at least one linking unitY³ or Y⁴ interposed between the radicals A¹ and A² and the centralmoiety (T¹-B¹-)_(m)-T³-C≡C-T⁴-(B²-T²-)_(n) (also designated M below) isa —O—CO—O—, —O—CO—N(R)—, —(R)N—CO—O— or —(R)N—CO—N(R)— group. The otherlinking unit may be any group listed under the meaning of Y¹ to Y⁴.

Preferred compounds of the formula I according to the invention have,even taking into account the abovementioned preferences, at least one—O—CO—O— group as linking unit Y³ or Y⁴, where the other linking unitmay again be any group listed under the meaning of Y¹ to Y⁴.

Particularly preferred compounds of the formula I are, even when takinginto account the abovementioned preferences, those in which both linkingunits Y³ and Y⁴ are a —O—CO—O— group.

Further preferred compounds of the formula I are, even taking intoaccount the abovementioned preferences, those in which the sum of thevariables m and n is 0 or 1. Therefore, the central unit M preferablycomprises two or three divalent saturated or unsaturated carbocyclic orheterocyclic radicals T. Examples of such preferred radicals T¹ to T⁴have already been mentioned above.

Preferred compounds of the formula I are furthermore, even taking intoaccount the abovementioned preferences, those in which at least one ofthe radicals P¹ or P² is a polymerizable group or a group suitable forpolymerization or a radical which carries a polymerizable group or agroup suitable for polymerization. Corresponding reactive radicals andtheir preferences, also with respect to the linking units Y¹ and Y²,have likewise been mentioned above.

The alkyne compounds of the formula I according to the invention areprepared by conventional methods.

One route which is possible in principle is the construction of thecentral moiety (T¹-B¹-)_(m)-T³-C≡C-T⁴-(B²-T²-)_(n) by means of aSonogashira reaction using starting materials which comprisecorresponding molecule fragments (T¹-B¹-)_(m)-T³-C≡C—H andHal-T⁴-(B²-T²-)_(n) or (T¹-B¹-)_(m)-T³-Hal and H—C≡C-T⁴-(B²-T²-)_(n),where Hal is halogen, preferably iodine. The resulting intermediatecompounds are then reacted further to give the target compounds of theformula I by conventional synthetic methods.

Another route involves reacting corresponding starting materials bymeans of a Sonogashira reaction which already comprise additionalmolecule fragments P¹—Y¹-A¹-Y³- and/or -Y⁴-A²-Y²—P². For example, toproduce the target compounds of the formula I, compounds of the generalformula P¹—Y¹-A¹-Y³-(T¹-B¹-)_(m)-T³-C≡C—H can be reacted with compoundsof the general formula Hal-T⁴-(B²-T²-)_(n)-Y⁴-A²-Y²—P², compounds of thegeneral formula P¹—Y¹-A¹-Y³-(T¹-B¹-)_(m)-T³-C≡C—H can be reacted withcompounds comprising fragments of the general formulaHal-T⁴-(B²-T²-)_(n), or compounds which comprise fragments of thegeneral formula (T¹-B¹-)_(m)-T³-C≡C—H can be reacted with compounds ofthe general formula Hal-T⁴-(B²-T²-)_(n)-Y⁴-A²-Y²-P². The alkynyl radical—C≡C—H and the halogen atom Hal can of course also in each case be inthe other compound or the other fragment, respectively.

The starting alkyne compound, for example (T¹-B¹-)_(m)-T³-C≡C—H orP¹—Y¹-A¹-Y³-(T¹-B¹-)_(m)-T³-C≡C—H, and the starting halogen compound,for example Hal-T⁴-(B²-T²-)_(n) or Hal-T⁴-(B²-T²-)_(n)-Y⁴-A²-Y²—P², areusually employed in a molar ratio of 1:1.

According to retrosynthetic considerations, it may be useful to produce,in a first step, e.g. alkyne compounds comprising the fragments-A¹-Y³-(T¹-B¹-)_(m)-T³-C≡C-T⁴-(B²-T²-)_(n)-Y⁴-A²-Y²—P²,P¹—Y¹-A¹-Y³-(T¹-B¹)_(m)-T³-C≡C-T⁴-(B²-T²-)_(n)-Y⁴-A²-,-A¹-Y³-(T¹-B¹-)_(m)-T³-C≡C-T⁴-(B²-T²-)_(n)-Y⁴-A²-,-A¹-Y³-(T¹-B¹-)_(m)-T³-C≡C-T⁴-(B²-T²-)_(n)- or-(T¹-B¹-)_(m)-T³-C≡C-T⁴-(B²-T²-)_(n)-Y⁴-A²and to convert these compounds into the target compounds of the formulaI with the corresponding complementary compounds in one or moresubsequent steps.

If P¹ and/or P² are reactive radicals which are unstable under theconditions of a Songashira reaction, it is possible, for example to usesuitable starting compoundsP¹′-Y¹-A¹-Y³-(T¹-B¹-)_(m)-T³-Hal and/orH—C≡C-T⁴-(B²-T²-)_(n)-Y⁴-A²-Y²-P²′in which the radicals P¹′ and/or P²′ denote precursor groups which arestable under the reaction conditions. The latter groups can then beconverted into the corresponding reactive radicals P¹ and/or P² in asubsequent step.

The present invention further provides nonpolymerizableliquid-crystalline compositions comprising at least one compound f theformula I or a preferred embodiment thereof.

Nonpolymerizable liquid-crystalline compositions for the purposes of thepresent invention are in particular those compositions which are notcapable of forming self-supporting polymerization or condensationproducts under conventional conditions. These compositions can beprepared, for example, by mixing suitable commercially availableliquid-crystalline materials as used, for example, for active LC layersin display technology with one or more of the compounds according to theinvention. These compositions may comprise compounds, in particularthose of the formula I with reactive radicals, the reactive radicalconcentration however not being sufficient to produce correspondinglydensely crosslinked self-supporting polymerization or condensationproducts. Accordingly, in such nonpolymerizable compositions, preferenceis given to using compounds of the formula I in which P¹ and P² informula I are each hydrogen or C₁-C₁₂-alkyl.

The invention furthermore provides polymerizable liquid-crystallinecompositions comprising at least one compound of the formula I or apreferred embodiment thereof.

These are in particular those compositions in which at least one of thecomponents is capable of forming polymerization or condensation productsunder conventional conditions. This component does not necessarily haveto be a polymerizable compound of the formula I according to theinvention. It is only necessary for the liquid-crystalline compositionto be polymerizable as such and to be polymerizable or condensable togive self-supporting products.

The desired degree of polymerization, crosslinking and/or condensationafter polymerization or condensation is complete may be controlleddepending on the number of reactive radicals in the components of thesepolymerizable liquid-crystalline compositions. In such compositions, thecompounds of the formula I according to the invention generally have atleast one, usually even two, reactive radicals P. These compounds areeasily obtainable by mixing suitable polymerizable, liquid-crystallinematerials with one or more of the compounds according to the invention.Suitable polymerizable, liquid-crystalline compounds are described, forexample, in WO 95/22586, 95/24454, 95/24455, 96/04351, 96/24647,97/00600, 97/34862 and 98/47979 and EP 1 134 270 A1 and DE 198 35 730 Aland have essentially the schematic structure P—Y-A-Y-M-Y-A-Y—P, where P,Y and A have the same meanings as P¹ and P², Y¹ to Y⁴ and A¹ and A² informula I. M denotes a mesogenic moiety similar to the central moiety(T¹-B¹-)_(m)-T³-C≡C-T⁴- -(B²-T²-)_(n) in formula I which is likewiseabbreviated as M in this application.

The nonpolymerizable and polymerizable liquid-crystalline compositionsaccording to the invention may of course comprise one or more alkynederivatives as components which are described in the documents listed atthe outset. A person skilled in the art may usually select suitablecompounds according to whether nonpolymerizable or polymerizablecompositions are to be adjusted.

The nonpolymerizable and polymerizable liquid-crystalline compositionsaccording to the invention are not limited to those compositions inwhich one or more constituents have liquid-crystalline properties per se(in the temperature range of interest), but also include thosecompositions in which liquid-crystalline behavior is only achieved bymixing the components or by admixing of the compounds according to theinvention (e.g. lyotropic systems). Furthermore, the compounds of theformula I according to the invention and preferred embodiments thereofmay themselves exhibit liquid-crystalline behavior, but do notnecessarily have to exhibit this property.

The reactive compounds which are listed in DE 100 25 782 A1 as componentB) of the liquid-crystalline compositions of matter described thereinmay also be added to the polymerizable liquid-crystalline compositionsaccording to the invention. These mostly low-cost compounds usually donot exhibit liquid-crystalline behavior themselves, but their admixturemakes it possible to reduce the proportion of costly compounds in thecompositions according to the invention without having a noticeableeffect on the liquid-crystalline behavior of the compositions. By meansof such reactive compounds, it is furthermore possible to tailorproperties of the compositions, such as degree of crosslinking,viscosity, elasticity etc. The person skilled in the art may easilyselect suitable reactive compounds, if necessary after preliminaryexperiments. It should be noted that such reactive compounds may alsoact as (auxiliary) compounds as discussed above.

Depending on the intended use, the nonpolymerizable and polymerizableliquid-crystalline compositions according to the invention mayfurthermore comprise at least one chiral compound. The addition ofchiral compounds leads to cholesteric compositions which have specialoptical properties, for example viewing angle-dependent color effects,reflection in the IR or UV wavelength range of the spectrum etc.

Preferred chiral compounds correspond to the general formulae Ia to Id(P³—Y⁵-)_(p)X  Ia,(P³—Y⁵-A³-Y⁶—)_(p)X  Ib,(P³—Y⁵—)_(p)X  Ic,(P³—Y⁵-A³-Y⁶-M′-Y⁷—)_(p)X  Id,in which M′ is a mesogenic group (T⁵-B³-)_(q)-T⁶ and P³, Y⁵ to Y⁷, A³,T⁵ and T⁶ and B³ have the same meaning as P¹ and P², Y¹ to Y⁴, A¹ andA², T¹ to T⁴ and B¹ and B² in the formula I. p is 1, 2, 3, 4, 5 or 6 andX is the corresponding n-valent chiral radical. The p groups attached tothe chiral radical X may be identical or different.

Possible radicals X are, for example:

where

-   L is R′, R′O, COOR′, OCOR′, CONHR′ or NHCOR′, halogen, in particular    fluorine, chlorine or bromine, and R′ is C₁-C₄-alkyl, for example    methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, tert-butyl.-   X is particularly preferably:

Preferred mesogenic groups M′ in the chiral compounds of the formula Idare:

where j′ and j″ are 0 or 1.

Further chiral compounds containing these and other suitable chiralradicals X are mentioned, for example, in WO 95/16007, EP 0 747 382 A1,EP 0 750 029 A1, EP 1 136 478 A1 and DE 198 43 724 A1.

The present invention provides the use of the nonpolymerizable andpolymerizable liquid-crystalline compositions for producing opticalcomponents, such as LCDs, polarizers or filters.

The present invention furthermore provides such optical components whichhave been obtained using the nonpolymerizable and polymerizableliquid-crystalline compositions.

The polymerizable liquid-crystalline compositions according to theinvention can furthermore be used for printing or coating substrates.These compositions may comprise further additives. Suitable additivesinclude additives selected from the group consisting of:

1) photoinitiators,

2) diluents,

3) additives selected from the group consisting of:

-   -   a) antifoams and deaerators,    -   b) lubricants and flow auxiliaries,    -   c) thermally curing or radiation-curing auxiliaries,    -   d) substrate wetting auxiliaries,    -   e) wetting and dispersion auxiliaries,    -   f) hydrophobicizing agents and    -   g) adhesion promoters and auxiliaries for improving the scratch        resistance,

4) additives selected from the group consisting of:

-   -   a) dyes and    -   b) pigments, and

5) additives selected from the group consisting of light, heat and/oroxidation stabilizers.

The chemicophysical nature of these additives is described in detail inWO 00/47694.

The present invention furthermore provides printed or coated substrateswhich have been produced using the polymerizable compositions accordingto the invention, if desired in admixture with the abovementionedadditives.

Examples of such substrates are paper and cardboard products, forexample for carrier bags, magazines, brochures, gift wrappings andpackaging materials for consumables, food products and luxury products,sheets, for example for decorative or non-decorative packaging, textilesof any kind and leather. Further suitable substrates are materials usedfor producing banknotes, securities, admission tickets and the like.

Further substrates are (consumer) electronic products, such as musiccassettes (MCs), SVHS and VHS cassettes, minidiscs (MDs), compact discs(CDs), digital versatile discs (DVDs) and the corresponding reproductionand/or recording equipment, televisions, radios, telephone/mobilephones, electronic data processing equipment etc. and products from theleisure, sports, domestic and games sector, for example bicycles,childrens vehicles, skis, snowboards and surfboards, in-line skates,roller skates and ice-skates and domestic appliances. Such substratesfurthermore include writing utensils and spectacle frames, for example.

Other substrates are surfaces encountered in the construction sector,such as building walls or windowpanes. In the latter case, a functionaleffect may be desired in addition to a decorative effect. Thus, it ispossible to produce multilayers on the window material whose individuallayers have different chemicophysical properties. If, for exampleindividual layers of the polymerizable liquid-crystalline compositionshaving opposite twist (by adding one enantiomer of a chiral compound andthe corresponding optical antipode) or individual layers of crosslinkedcholesteric liquid-crystalline compositions having the same helicalhandedness but different pitch and thus different reflection properties(by adding different concentrations of chiral compound) are applied,specific wavelengths or wavelength ranges of the light spectrum can bereflected in a controlled manner. In this way it is possible forexample, to provide a window coating which is IR or UV reflective. Forthis aspect of the compositions according to the invention, inparticular heat-insulating coatings, reference is also made to WO99/19267.

The invention furthermore provides the use of the polymerizableliquid-crystalline compositions according to the invention for preparingdispersions and emulsions, which are preferably water-based. For thepreparation of such dispersions and emulsions, reference is made to WO96/02597 and 98/47979 which describe the preparation of dispersions andemulsions using liquid-crystalline materials.

Accordingly the present invention also provides such dispersions andemulsions which have been prepared using the polymerizableliquid-crystalline compositions according to the invention. Thesedispersions and emulsions can likewise be used for printing and coatingsubstrates as described above by way of example.

The present invention furthermore provides the use of the polymerizableliquid-crystalline compositions according to the invention for producingfilms. For the purposes of the present invention, such films are inparticular self-supporting layers as obtained by polymerizing thecompositions. These films may also be on substrates or backings suchthat the films can be removed and transferred to other substrates orbackings for permanent adhesion by appropriate measures. Such films canbe used, for example, in film coating and laminating processes.

Accordingly, the present invention furthermore provides such films whichhave been produced using the polymerizable liquid-crystallinecompositions according to the invention.

The present invention furthermore provides the use of the polymerizableliquid-crystalline compositions according to the invention for producingpigments.

The production of such pigments is known and described in detail in WO99/11733, for example. Furthermore, it is also possible to producepigments of predefined shape and size by using printing methods or bymeans of nets with gaps in which the polymerizable composition isplaced. The liquid-crystalline composition is then polymerized orcondensed followed by removal from the substrate or net. Theseprocedures are described in detail in WO 96/02597, 97/27251, 97/27252and EP 0 931 110 A1.

The polymerizable liquid-crystalline compositions are converted intopolymers having a frozen liquid-crystalline order structure with the aidof their reactive groups and, depending on their chemical nature, bycondensation or free-radical or ionic polymerization processes which canbe initiated by photochemical reaction.

These pigments may be single-layered or multilayered. However the latterpigments can usually only be obtained if coating processes are used inwhich a plurality of layers are formed successively on top of oneanother followed by a final mechanical comminution.

Accordingly, the present invention also provides pigments which havebeen prepared from such polymerizable liquid-crystalline compositionsaccording to the invention.

EXAMPLES Example 1

Synthesis of Compound 1 According to the Invention:

Synthesis of Compound 1a:

Dimethylformamide (DMF; 100 cm³) was admixed with 4-iodophenol (14.3 g,0.065 mol) and N,N-dimethylcyclohexylamine (DMCA; 24.7 g, 0.195 mol) andKerobit BHT (one spatula tip). Acryloyloxybutyl chloroformate (15.4 g,0.071 mol) was added dropwise at 0-5° C. The mixture was stirred for 3hours at 40° C. and 16 hours at room temperature and then poured onto 1m hydrochloric acid, extracted with methyl chloride and dried oversodium sulfate, and the solvent was removed.

Yield of compound 1a: 97.8% of theory.Synthesis of Target Compound 1:

DMF (42 cm³) was admixed with compound 1a (10.5 g, 0.027 mol),bis(triphenylphosphine)palladium(II) chloride (0.097 g, 0.5 mol % basedon the number of moles of compound 1a), copper(I) iodide (0.027 g, 0.5mol % based on the number of moles of compound 1a) and triethylamine (27cm³, 0.194 mol). Phenylacetylene (2.7 g, 0.027 mol) in DMF (50 cm³) wasadded dropwise at 40° C. under a nitrogen atmosphere. The mixture wasstirred for 5 hours at 50° C. and then poured onto 1 m hydrochloric acidand extracted with 500 cm³ of toluene, the toluene extract was driedover sodium sulfate and the solvent was removed. Column purification(silica gel, toluene) gave compound 1 in a yield of 20% of theory. Themelting point was 59-60° C.

Example 2

Synthesis of Compound 2 According to the Invention:

Synthesis of Compound 2a:

DMF (100 cm³) was admixed with 4-iodophenol (14.3 g, 0.065 mol) and DMCA(26.0 g, 0.205 mol). Butyl chloroformate (15.4 g, 0.071 mol) was addeddropwise at 0-5° C. The mixture was stirred for a further 3 hours at 40°C. and then poured onto 1 m hydrochloric acid (1 molar), extracted withtoluene and dried over sodium sulfate, and the solvent was removed.

Yield of compound 2a: 93.8% of theory.Synthesis of Target Compound 2:

DMF (42 cm³) was admixed with compound 2a (8.5 g, 0.027 mol),bis(triphenylphosphine)palladium(II) chloride (0.097 g, 0.5 mol % basedon the number of moles of compound 1a), copper(I) iodide (0.027 g, 0.5mol % based on the number of moles of compound 1a) and triethylamine (27cm³, 0.193 mol). Phenylacetylene (2.7 g, 0.027 mol) in DMF (50 cm³) wasadded dropwise at 40° C. under a nitrogen atmosphere. The mixture wasstirred for 5 hours at 50° C. and then poured onto 1 m hydrochloric acidand extracted with toluene (300 cm³), the toluene extract was dried oversodium sulfate and the solvent was removed. Column purification (silicagel, toluene) gave compound 2 in a yield of 64% of theory. The meltingpoint was 55-56° C.

Example 3

Synthesis of Compound 3 According to the Invention:

DMF (45 cm³) was admixed with compound 1a (11.9 g, 0.029 mol),bis(triphenylphosphine)palladium(II) chloride (0.105 g, 0.5 mol % basedon the number of moles of compound la), copper(I) iodide (0.029 g, 0.5mol % based on the number of moles of compound 1a) and triethylamine (29cm³, 0.21 mol). 4-Pentylphenylacetylene (5.0 g, 0.029 mol) in DMF (55cm³) was added dropwise at 40° C. under a nitrogen atmosphere. Themixture was stirred for 5 hours at 50° C. and then poured onto 1 mhydrochloric acid and extracted with ethyl chloride (300 cm³), theextract was dried over sodium sulfate and the solvent was removed.Purification by triturating with petroleum ether gave compound 3 in ayield of 37.6% of theory. The melting point was 60-67° C.

1. An alkyne compound of the formula IP¹—Y¹-A¹-Y³-(T¹-B¹-)_(m)-T³-C5C-T⁴-(B²-T²-)_(n)-Y⁴-A²-Y²-P²  (I) inwhich wherein P¹, P² are each, independently of one another, hydrogen,C₁-C₁₂-alkyl, a polymerizable group, a group suitable for polymerizationor a radical having a polymerizable group or a group suitable forpolymerization, Y¹, Y², Y³, Y⁴ are each, independently of one another, asingle chemical bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —CO—N(R)—,—(R)N—CO—, —O—CO—O—, —O—CO—N(R)—, —(R)N—CO—O— or —(R)N—CO—N(R)—, B¹, B²are each, independently of one another, —C5C—, a single chemical bond,—O—, —S—, —CO—, —CO—O—, —O—CO—, —CO—N(R)—, —(R)N—CO—, —O—CO—O—,—O—CO—N(R)—, —(R)N—CO—O— or —(R)N—CO—N(R)—, R, at each occurrence andindependently of the meaning in Y¹ to Y⁴, B¹ and B², is hydrogen orC₁-C₄-alkyl, A¹, A² are each, independently of one another, a singlechemical bond or a spacer having from one to 30 carbon atoms, T¹, T²,T³, T⁴ are each, independently of one another, a divalent saturated orunsaturated carbocyclic or heterocyclic radical, and m, n are each,independently of one another, 0 or 1, wherein at least one of thelinking units Y³ or Y⁴ is a —O—CO—O—, —O—CO—N(R)—, —(R)N—CO—O— or—(R)N—CO—N(R)—.
 2. The compound as claimed in claim 1, wherein T¹ to T⁴in formula I are selected from the group consisting of


3. The compound as claimed in claim 1, wherein at least one of Y³ or Y⁴in formula I is —O—CO—O—.
 4. The compound as claimed in claim 1, whereinY³ and Y⁴ in formula I are —O—CO—O—.
 5. The compound as claimed in claim1, wherein the sum of the variables m and n in formula I is 0 or
 1. 6.The compound as claimed in claim
 1. wherein at least one of the radicalsP¹ or P² in formula I is a polymerizable group, a group suitable forpolymerization or a radical having a polymerizable group or a groupsuitable for polymerization.
 7. A nonpolymerizable liquid-crystallinecomposition comprising at least one compound of the formula I as claimedin claim 1, wherein the liquid-crystalline composition is notpolymerizable.
 8. A polymerizable liquid-crystalline compositioncomprising at least one compound of the formula I as claimed in claim 1,wherein the liquid-crystalline composition is polyermizable.
 9. Anmethod of producing an optical component comprising forming an opticalcomponent with the composition as claimed in claim
 7. 10. An opticalcomponent a comprising the composition as claimed in claim
 7. 11. Amethod of printing or coating a substrate comprising: printing orcoating a substrate with the composition as claimed in claim
 8. 12. Aprinted or coated substrate comprising the composition as claimed inclaim
 8. 13. A method of preparing a dispersion or an emulsioncomprising: dispersing the composition as claimed in claim 8 in a liquidmedium to obtain the dispersion or the emulsion.
 14. A dispersion oremulsion comprising the composition as claimed in claim
 8. 15. A methodof producing a film comprising: forming the composition as claimed inclaim 8 into a film.
 16. A film comprising the a composition as claimedin claim
 8. 17. A method of producing a pigment comprising forming thepigment with the composition as claimed in claim
 8. 18. A pigmentcomprising the composition as claimed in claim
 8. 19. An method ofproducing an optical component comprising forming an optical componentwith the composition as claimed in claim
 8. 20. An optical componentcomprising the composition as claimed in claim 8.